NiCo<sub>2</sub>S<sub>4</sub>六角片作为钠离子电池负极材料的电化学性能及储钠动力学

引用本文: 赵明宇, 朱琳, 付博文, 江素华, 周永宁, 宋云. NiCo₂S₄六角片作为钠离子电池负极材料的电化学性能及储钠动力学[J]. 物理化学学报, 2019, 35(2): 193-199. doi: 10.3866/PKU.WHXB201801241 shu

Citation: ZHAO Mingyu, ZHU Lin, FU Bowen, JIANG Suhua, ZHOU Yongning, SONG Yun. Sodium Ion Storage Performance of NiCo₂S₄ Hexagonal Nanosheets[J]. Acta Physico-Chimica Sinica, 2019, 35(2): 193-199. doi: 10.3866/PKU.WHXB201801241 shu

NiCo₂S₄六角片作为钠离子电池负极材料的电化学性能及储钠动力学

复旦大学材料科学系，上海 200433

通讯作者: 宋云, songyun@fudan.edu.cn

基金项目:

国家自然科学基金(51601040，51572948，51502039)资助项目

摘要: 通过共沉淀以及后续的气相硫化成功制备了横向边长约为2 μm，纵向厚度约为30 nm的NiCo₂S₄六角片，并研究了其作为钠离子电池负极材料的电化学性能。电化学性能测试结果显示在1000 mA·g^-1的电流密度下，NiCo₂S₄电极循环60次后仍然可保持约387 mAh·g^-1的可逆比容量。此外，NiCo₂S₄电极还具有良好的倍率性能，在200、400、800、1000和2000 mA·g^-1的电流密度下，容量分别为542、398、347、300和217 mAh·g^-1。通过进一步动力学机制分析发现，NiCo₂S₄电极的良好的倍率性能得益于其二维片层状结构诱导产生的赝电容。上述结果表明，NiCo₂S₄纳米六角片是一种极具潜力的钠离子电池负极材料。

关键词:

English

Sodium Ion Storage Performance of NiCo₂S₄ Hexagonal Nanosheets

Department of Materials Science, Fudan University, Shanghai 200433, P. R. China

Corresponding author: SONG Yun, Email: songyun@fudan.edu.cn; Tel.: +86-21-65642380

Received Date: 11 January 2018
Accepted Date: 22 January 2018
Revised Date: 21 January 2018
Available Online: 15 January 2019
Fund Project:

The project was supported by the National Natural Science Foundation of China (51601040, 51572948, 51502039)

Abstract: As a potential substitute for commercial lithium ion batteries (LIBs), sodium ion batteries (NIBs) have attracted increasing interest during the last decade. However, compared to the LIBs, the sluggish kinetics of sodium ion diffusion in NIBs due to its larger ionic radius results in deteriorated electrochemical performances, which hinders the future development and application of NIBs. Therefore, exploring anode materials that exhibit a novel kinetic mechanism is desired. Recently, extremely rapid kinetics has been realized by introducing the pseudocapacitance effect into battery systems; this effect generally refers to faradaic charge-transfer reactions, including surface or near-surface redox reactions, and fast bulk ion intercalation. To obtain a pseudocapacitance effect in battery systems, the critical step involves the rational design of a two-dimensional structure with a high conductivity. In this regard, the bimetallic sulfide thiospinel NiCo₂S₄ stands out by virtue of its high conductivity (1.25 × 10⁶ S·m^-1) at room temperature, which is at least two orders of magnitude higher than that of the oxide counterpart (NiCo₂O₄). Herein, NiCo₂S₄ hexagonal nanosheets with a large lateral dimension of ~2 μm and thickness ~30 nm have been successfully synthesized through coprecipitation followed by a vapor sulfidation method. As the anode material in NIBs, the NiCo₂S₄ nanosheets deliver a reversible capacity of 387 mAh·g^-1 after 60 cycles at a current density of 1000 mA·g^-1. Additionally, the NiCo₂S₄ nanosheets exhibit high reversible capacities of 542, 398, 347, 300, and 217 mAh·g^-1 at the current densities 200, 400, 800, 1000, and 2000 mA·g^-1, respectively. Ex situ X-ray diffraction analysis has been employed to reveal that the sodium ion storage process is a result of a combined Na⁺ intercalation and conversion reaction between Na⁺ and NiCo₂S₄. Further quantitative analysis of the kinetics has verified the extrinsic pseudocapacitance mechanism of the Na⁺ storage process, in which the capacitive contribution enlarges as the current density increases. The observed capacitive contribution of NiCo₂S₄ electrode is as high as 71% at a scan rate of 0.4 mV·s^-1. This is closely attributed to the modified thin-sheet structure of NiCo₂S₄ and hybridization with graphene that account for the superior high-rate performance with long-term cyclability. These intriguing results shed light on a new strategy for the structural design of electrode materials for advanced NIBs. Moreover, this vapor transformation route can be extended to the preparation of other transition metal disulfides with high electrochemical activities, such as FeCo₂S₄, ZnCo₂S₄, CuCo₂S₄, etc.

Key words:

1. [1]
  Le, Y.; Yang, J. F.; Lou, X. W. Angew. Chem. Int. Ed. 2016, 55, 13422. doi: 10.1002/anie.201606776
2. [2]
  Chen, Y. M.; Yu, Y. M.; Li, Z.; Paik, U.; Lou, X. W. Sci. Adv. 2016, 2, 1600021. doi: 10.1126/sciadv.1600021
3. [3]
  Ye, J.; Chen, T.; Chen, Q.; Chen, W.; Yu, Z.; Xu, S. J. Mater. Chem. A 2016, 4, 13194. doi: 10.1039/c6ta04196e
4. [4]
  Zhu, Y. J.; Fan, X. L.; Suo, L. M.; Luo, C.; Gao, T.; Wang, C. S. ACS Nano 2016, 10, 1529. doi: 10.1021/acsnano.5b07081
5. [5]
  Li, X.; Zai, J.; Xiang, S.; Liu, Y.; He, X.; Xu, Z.; Wang, K.; Ma, Z.; Qian, X. Adv. Energy Mater. 2016, 6, 1601056. doi: 10.1002/aenm.201601056
6. [6]
  Cabana, J.; Monconduit, L.; Larcher, D.; Palacín, M. R. Adv. Mater. 2010, 22, E170. doi: 10.1002/adma.201000717
7. [7]
  Kim, H.; Kim, D. J.; Seo, D. H.; Yeom, M. S.; Kang, K.; Kim, D. K.; Jung, Y. Chem. Mater. 2012, 24, 1205. doi: 10.1021/cm300065y
8. [8]
  Zhu, Y. J.; Choi, S. H.; Fan, X. L.; Shin, J.; Ma, Z. H.; Zachariah, M. R.; Jang, W. C.; Wang, C. S. Adv. Energy Mater. 2017, 7, 1601578. doi: 10.1002/aenm.201601578
9. [9]
  Lee, E.; Brown, D. E.; Alp, E. E.; Ren, Y.; Lu, J.; Woo, J. J.; Johnson, C. S. Chem. Mater. 2015, 27, 6755. doi: 10.1021/acs.chemmater.5b02918
10. [10]
  Liu, H.; Jia, M. Q.; Zhu, Q. Z.; Cao, B.; Chen, R. J.; Wang, Y.; Wu, F.; Xu, B. ACS Appl. Mater. Interfaces 2016, 8, 26878. doi: 10.1021/acsami.6b09496
11. [11]
  Jache, B.; Adelhelm, P. Angew. Chem. Int. Ed. 2014, 53, 10169. doi: 10.1002/anie.201403734
12. [12]
  Che, H.; Chen, S.; Xie, Y.; Wang, H.; Amine, K.; Liao, X.; Ma, Z. Energy Environ. Sci. 2017, 10, 1075. doi: 10.1039/C7EE00524E
13. [13]
  Li, T.; Xu, Y.; Xing, F.; Cao, X.; Bian, J.; Wang, N.; Wang, Z. L. Adv. Energy Mater. 2017, 7, 1700124. doi: 10.1002/aenm.201700124
14. [14]
  Zou, R.; Zhang, Z.; Yuen, M. F.; Sun, M.; Hu, J.; Lee, C. S.; Zhang, W. NPG Asia Mater. 2015, 7, 195. doi: 10.1038/am.2015.63
15. [15]
  Kang, W.; Wang, Y.; Xu, J. J. Mater. Chem. A 2017, 5, 7667. doi: 10.1039/C7TA00003K
16. [16]
  Chen, S.; Qiao, S. Z. ACS Nano 2013, 7, 10190. doi: 10.1021/nn404444r
17. [17]
  Wu, X.; Li, S.; Wang, B.; Liu, J.; Yu, M. Phys. Chem. Chem. Phys. 2017, 19, 11554. doi: 10.1039/C7CP00509A
18. [18]
  Yuan, D. X.; Huang, G.; Yin, D. M.; Wang, X. X.; Wang, C. L.; Wang, L. M. ACS Appl. Mater. Interfaces 2017, 9, 18178. doi: 10.1021/acsami.7b02176
19. [19]
  Xiao, Y.; Lee, S. H.; Sun, Y. K. Adv. Energy Mater. 2016, 7, 1601329. doi: 10.1002/aenm.201601329
20. [20]
  Chen, S. Q.; Wu, S.; Shen, L. F.; Zhu, C. B.; Huang, Y. Y.; Xi, K.; Maier, J.; Yu, Y. Adv. Mater. 2017, 1700431. doi: 10.1002/adma.201700431
21. [21]
  刘家辉, 张辉, 崔艳华, 刘效疆, 刘劲松. 无机化学学报, 2015, 32, 2331 doi: 10.11826/CJIC.2015.306Liu, J. H. ; Zhang, H. ; Liu, X. J. ; Liu, J. S. Inorg. Chem. 2015, 32, 2331.
22. [22]
  Kyle, C. K.; Stephany, G.; Naween, D.; Jonathan, L. S.; Souza, J. P.; Trevor, H. C.; Mark, A. C.; Adam, H.; Simon, M. H.; Mullins, B. C. J. Mater. Chem. A 2014, 2, 14209. doi: 10.1039/c4ta02684e
23. [23]
  Hu, T. T.; Liu, Z. G.; Borkiewicz, O. J.; Cheng, J.; Hua, X.; Dunstan, M. T.; Yu, X. Q.; Wiaderek, K.M.; Du, L. S.; Chapman, K. W.; et al. Nat. Mater. 2013, 12, 1130. doi: 10.1038/NMAT3784
24. [24]
  李婷, 龙志辉, 张道洪.物理化学学报, 2016, 32, 573 doi: 10.3866/PKU.WHXB201511105Li, T.; Long, Z. H.; Zhang, D. H. Acta Phys. -Chim. Sin. 2016, 32, 573. doi: 10.3866/PKU.WHXB201511105
25. [25]
  Slater, M. D.; Kim, D.; Lee, E.; Johnson, C. S. Adv. Funct. Mater. 2013, 23, 947. doi: 10.1002/adfm.v23.8
26. [26]
  Song, Y.; Chen, Z.; Li, Y.; Qin, C.W.; Fang, F.; Zhou, Y.; Hu, L.; Sun, D. J. Mater. Chem. A 2017, 5, 9022. doi: 10.1039/C7TA01758H
27. [27]
  Wu, X.; Li, S.; Wang, B.; Liu, J.; Yu, M. Phys. Chem. Chem. Phys. 2016, 18, 4505. doi: 10.1039/c5cp07541f
28. [28]
  Song, Y.; Cao, Y.; Wang, J.; Zhou, Y. N.; Fang, F.; Li, Y.; Gao, S. P.; Gu, Q. F.; Hu, L.; Sun, D. ACS Appl. Mater. Interfaces 2016, 3, 21334. doi: 10.1021/acsami.6b05506
29. [29]
  Brezensinski, T.; Wang, J.; Tolbert, S. H.; Dunn, B. Nat. Mater. 2010, 9, 146. doi: 10.1038/nmat2612
30. [30]
  Sun, R. M.; Wei, Q. L.; Sheng, J. Z.; Shi, C. W.; An, Q. Y.; Lin, S. J.; Mai, L. Q. Nano Energy 2017, 35, 396. doi: 10.1016/j.nanoen.2017.03.036
31. [31]
  Simon, P.; Gogotsi, Y.; Dunn, B. Science 2014, 343, 1210. doi: 10.1126/science.1249625
32. [32]
  Chao, D. L.; Zhu, C. R.; Yang, P. H.; Xia, X. H.; Liu, J. L.; Wang, J.; Fan, X. F.; Savilov, S. V.; Lin, J. Y.; Fan, H. J.; et al. Nat. Commun. 2016, 7, 12122. doi: 10.1038/ncomms12122

扫一扫看文章

计量

PDF下载量: 24
文章访问数: 1545
HTML全文浏览量: 226

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

NiCo₂S₄六角片作为钠离子电池负极材料的电化学性能及储钠动力学

通讯作者: 宋云, songyun@fudan.edu.cn

English

Sodium Ion Storage Performance of NiCo₂S₄ Hexagonal Nanosheets

Corresponding author: SONG Yun, Email: songyun@fudan.edu.cn; Tel.: +86-21-65642380

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

NiCo2S4六角片作为钠离子电池负极材料的电化学性能及储钠动力学

通讯作者: 宋云, songyun@fudan.edu.cn

English

Sodium Ion Storage Performance of NiCo2S4 Hexagonal Nanosheets

Corresponding author: SONG Yun, Email: songyun@fudan.edu.cn; Tel.: +86-21-65642380

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

NiCo₂S₄六角片作为钠离子电池负极材料的电化学性能及储钠动力学

Sodium Ion Storage Performance of NiCo₂S₄ Hexagonal Nanosheets

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs